WO2018055882A1 - 非水系二次電池用セパレータ及び非水系二次電池 - Google Patents

非水系二次電池用セパレータ及び非水系二次電池 Download PDF

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Publication number
WO2018055882A1
WO2018055882A1 PCT/JP2017/025813 JP2017025813W WO2018055882A1 WO 2018055882 A1 WO2018055882 A1 WO 2018055882A1 JP 2017025813 W JP2017025813 W JP 2017025813W WO 2018055882 A1 WO2018055882 A1 WO 2018055882A1
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WIPO (PCT)
Prior art keywords
porous layer
resin
separator
mass
porous
Prior art date
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PCT/JP2017/025813
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English (en)
French (fr)
Japanese (ja)
Inventor
貴 中広
本多　勧
Original Assignee
帝人株式会社
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Publication date
Application filed by 帝人株式会社 filed Critical 帝人株式会社
Priority to JP2017554611A priority Critical patent/JP6334071B1/ja
Priority to CN201780048839.4A priority patent/CN109565021B/zh
Priority to KR1020197003617A priority patent/KR102434168B1/ko
Publication of WO2018055882A1 publication Critical patent/WO2018055882A1/ja

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Definitions

  • the present invention relates to a separator for a non-aqueous secondary battery and a non-aqueous secondary battery.
  • Non-aqueous secondary batteries represented by lithium ion secondary batteries are widely used as power sources for portable electronic devices such as notebook computers, mobile phones, digital cameras, and camcorders.
  • portable electronic devices such as notebook computers, mobile phones, digital cameras, and camcorders.
  • the non-aqueous secondary battery exterior has been simplified and reduced in weight, and aluminum cans have been developed instead of stainless steel cans as exterior materials.
  • packs made of aluminum laminate film have been developed.
  • an aluminum laminate film pack is soft, a battery (so-called soft pack battery) using the pack as an outer packaging material (a so-called soft pack battery) has an electrode and a separator formed by impact from the outside or expansion and contraction of the electrode accompanying charge / discharge. A gap is easily formed between the two, and the cycle life of the battery may be reduced.
  • dry heat press heat press treatment without impregnating the electrolyte in the separator
  • the laminate in which the separator is disposed between the positive electrode and the negative electrode for the purpose of improving the manufacturing yield of the battery. May be applied.
  • a separator excellent in adhesion between the positive electrode and the negative electrode by dry heat press is desired.
  • the present disclosure is a separator provided with a porous layer containing a polyvinylidene fluoride resin on both surfaces of a porous substrate, and is excellent in adhesion to a positive electrode and a negative electrode by dry heat press. It aims at providing the separator for batteries, and makes it a subject to solve this.
  • the present disclosure provides, as a second embodiment, a separator provided with an adhesive porous layer containing a polyvinylidene fluoride-based resin, which is excellent in adhesion to an electrode by dry heat press, for a non-aqueous secondary battery.
  • the purpose is to solve this.
  • the first form of the present disclosure includes the following forms.
  • a second porous layer comprising a layer, and a porous layer provided on the other surface of the porous substrate, the polyvinylidene fluoride resin and a resin having a glass transition temperature of 30 ° C. to 120 ° C. And a separator for a non-aqueous secondary battery.
  • the second porous layer wherein the polyvinylidene fluoride resin and the resin having a glass transition temperature of 30 ° C. to 120 ° C. are included in a compatible state. Separator for non-aqueous secondary battery.
  • the content of the resin having a glass transition temperature of 30 ° C. to 120 ° C. in the second porous layer is 5% by mass to 50% by mass of the total amount of all resins contained in the second porous layer. %, The separator for non-aqueous secondary batteries according to [1] or [2].
  • the first porous layer further contains an inorganic filler, and the content of the inorganic filler in the first porous layer is the total resin and the inorganic contained in the first porous layer.
  • the second porous layer further contains an inorganic filler, and the content of the inorganic filler in the second porous layer is the total resin and the inorganic contained in the second porous layer.
  • the resin having a glass transition temperature of 30 ° C. to 120 ° C. is at least one selected from the group consisting of acrylic resins, vinyl acetate resins and vinyl chloride resins.
  • the separator for non-aqueous secondary batteries in any one of. [7] A positive electrode, a negative electrode, and the separator for a nonaqueous secondary battery according to any one of [1] to [6] disposed between the positive electrode and the negative electrode. A non-aqueous secondary battery that obtains an electromotive force by doping.
  • the second embodiment of the present disclosure includes the following embodiments.
  • a porous substrate and an adhesive porous layer provided on one or both surfaces of the porous substrate comprising a vinylidene fluoride monomer unit and a hexafluoropropylene monomer unit, A polyvinylidene fluoride resin having a hexafluoropropylene monomer unit content of 5% by mass to 20% by mass of the total monomer units and a weight average molecular weight of 100,000 to 1,500,000, and a glass transition temperature of A separator for a non-aqueous secondary battery comprising an adhesive porous layer containing a resin having a temperature of 30 ° C to 120 ° C.
  • the content of the resin having a glass transition temperature of 30 ° C. to 120 ° C. in the adhesive porous layer is 5% by mass to 50% by mass of the total amount of all the resins contained in the adhesive porous layer.
  • the adhesive porous layer further contains an inorganic filler, and the content of the inorganic filler in the adhesive porous layer is the sum of the total resin and the inorganic filler contained in the adhesive porous layer.
  • the separator for a non-aqueous secondary battery according to any one of [11] to [13], which is 5 to 75% by mass of the amount.
  • the resin having a glass transition temperature of 30 ° C. to 120 ° C. is at least one selected from the group consisting of acrylic resins, vinyl acetate resins and vinyl chloride resins.
  • the separator for non-aqueous secondary batteries in any one of.
  • a separator having a porous layer containing a polyvinylidene fluoride-based resin on both surfaces of a porous base material, which is excellent in adhesion between a positive electrode and a negative electrode by dry heat press.
  • a separator for a secondary battery is provided.
  • a separator provided with an adhesive porous layer containing a polyvinylidene fluoride-based resin, which is excellent in adhesion to an electrode by dry heat press, is provided for a non-aqueous secondary battery separator.
  • process is not only an independent process, but is included in this term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
  • the amount of each component in the composition when there are a plurality of substances corresponding to each component in the composition, the plurality of the substances present in the composition unless otherwise specified. It means the total amount of substance.
  • machine direction means the long direction in the porous substrate and separator manufactured in a long shape
  • width direction means the direction orthogonal to the “machine direction”.
  • machine direction is also referred to as “MD direction”
  • width direction is also referred to as “TD direction”.
  • the “monomer unit” of the polyvinylidene fluoride resin means a constituent unit of the polyvinylidene fluoride resin, which is obtained by polymerizing the monomers.
  • a separator for a non-aqueous secondary battery of a first form (also referred to as a “first form of separator”) includes a porous substrate and a first porous layer provided on one surface of the porous substrate. And a second porous layer provided on the other surface of the porous substrate.
  • the first porous layer and the second porous layer exist as outermost layers of the separator and are layers that adhere to the electrode.
  • the first porous layer has a vinylidene fluoride monomer unit and a hexafluoropropylene monomer unit, and the content of the hexafluoropropylene monomer unit is all monomer units.
  • a polyvinylidene fluoride resin having a mass average molecular weight of 100,000 to 1,500,000 is contained.
  • the second porous layer contains a polyvinylidene fluoride-based resin and a resin having a glass transition temperature of 30 ° C. to 120 ° C.
  • VDF unit a vinylidene fluoride monomer unit
  • HFP unit a hexafluoropropylene monomer unit
  • HFP-HFP co-polymer a polyvinylidene fluoride resin having a VDF unit and an HFP unit
  • VDF-HFP co-polymer A VDF-HFP copolymer having a content of HFP units of 3% to 20% by mass of the total monomer units and a weight average molecular weight of 100,000 to 1,500,000 is referred to as “specific VDF- Also referred to as “HFP copolymer (1)”.
  • the separator of the first form includes a first porous layer containing the specific VDF-HFP copolymer (1), a polyvinylidene fluoride resin, and a resin containing a glass transition temperature of 30 ° C. to 120 ° C.
  • the separator of the first form has a first porous layer containing the specific VDF-HFP copolymer (1) on one surface for the following reasons, and has a glass transition temperature of 30 ° C. with the polyvinylidene fluoride resin.
  • a second porous layer containing a resin at ⁇ 120 ° C. is provided on the other side.
  • the positive electrode generally has a structure in which a positive electrode active material layer including a positive electrode active material and a binder resin is disposed on a current collector.
  • a binder resin of the positive electrode active material layer a polyvinylidene fluoride resin is mainly used. Used.
  • the negative electrode generally has a structure in which a negative electrode active material layer including a negative electrode active material and a binder resin is disposed on a current collector, and the binder resin of the negative electrode active material layer is mainly styrene butadiene rubber or Polyvinylidene fluoride resin is used.
  • the combination of the binder resin for the positive electrode and the binder resin for the negative electrode includes a form in which both are mainly polyvinylidene fluoride resins and a form in which one is mainly polyvinylidene fluoride resins and the other is mainly styrene butadiene rubber.
  • the first type of separator includes a VDF-HFP copolymer as a polyvinylidene fluoride resin in the first porous layer.
  • the HFP unit content of the VDF-HFP copolymer is 3% by mass or more, the mobility of the polymer chain is high when dry heat pressing is performed, and the polymer chain enters the unevenness of the electrode surface, thereby exhibiting an anchor effect. And improving the adhesion of the first porous layer to the electrode.
  • the HFP unit content of the VDF-HFP copolymer is 3% by mass or more, more preferably 5% by mass or more, and further preferably 6% by mass or more.
  • the HFP unit content of the VDF-HFP copolymer is 20% by mass or less, more preferably 18% by mass or less, and further preferably 15% by mass or less.
  • the range of the weight average molecular weight of the VDF-HFP copolymer is controlled as follows.
  • the first porous layer can secure mechanical properties that can withstand the adhesion treatment with the electrode, and the adhesion with the electrode is good. Further, if the Mw of the VDF-HFP copolymer is 100,000 or more, it is difficult to dissolve in the electrolytic solution, so that the adhesion between the electrode and the first porous layer is maintained inside the battery. From these viewpoints, the MDF of the VDF-HFP copolymer is 100,000 or more, more preferably 200,000 or more, further preferably 300,000 or more, and further preferably 500,000 or more.
  • the Mw of the VDF-HFP copolymer When the Mw of the VDF-HFP copolymer is 1.5 million or less, the viscosity of the coating liquid used for coating the first porous layer does not become too high, and the moldability and crystal formation are good. The surface property of the porous layer is highly uniform, and as a result, the adhesion of the first porous layer to the electrode is good. In addition, when the Mw of the VDF-HFP copolymer is 1,500,000 or less, the polymer chain has high mobility when dry heat pressing is performed, the polymer chain enters the irregularities of the electrode surface, and an anchor effect is exhibited. Improve adhesion of the first porous layer to the electrode. From these viewpoints, the Mw of the VDF-HFP copolymer is 1.5 million or less, more preferably 1.2 million or less, and still more preferably 1 million or less.
  • the second porous layer contains a polyvinylidene fluoride resin and a resin having a glass transition temperature of 30 ° C. to 120 ° C.
  • a resin having a glass transition temperature of 30 ° C. to 120 ° C. enhances the fluidity of the second porous layer during dry heat pressing, so that a polymer chain enters the irregularities on the electrode surface, and an anchor effect is exhibited, and the electrode Improve the adhesion of the second porous layer to.
  • the glass transition temperature of the resin having a glass transition temperature of 30 ° C. to 120 ° C. is 120 ° C. or less, more preferably 115 ° C. or less, more preferably 110 ° C. or less, from the viewpoint of developing fluidity by heat application of a dry heat press. More preferably, from the viewpoint of ensuring the heat resistance of the second porous layer, it is 30 ° C. or higher, more preferably 35 ° C. or higher, and even more preferably 40 ° C. or higher.
  • the first porous layer and the second porous layer is opposed to the positive electrode and the other is opposed to the negative electrode.
  • Either of the porous layers may be opposed to the positive electrode, and may be selected according to the material of the positive electrode active material layer or the material of the negative electrode active material layer.
  • the positive electrode active material layer includes a polyvinylidene fluoride resin as a binder resin
  • the negative electrode active material layer includes styrene butadiene rubber as a binder resin
  • the first-type separator has the first porous layer as the positive electrode.
  • the second porous layer is preferably disposed so as to face the negative electrode.
  • the separator according to the first embodiment is excellent in adhesion between the positive electrode and the negative electrode by dry heat press, and therefore, the separator is less likely to be misaligned with the electrode in the battery manufacturing process, thereby improving the battery manufacturing yield.
  • the first type of separator improves the cycle characteristics (capacity retention rate) of the battery because it is excellent in adhesion between the positive electrode and the negative electrode by dry heat pressing.
  • porous substrate the first porous layer, and the second porous layer included in the first-type separator will be described.
  • the porous substrate means a substrate having pores or voids therein.
  • a substrate include a microporous film; a porous sheet made of a fibrous material such as a nonwoven fabric and paper; a composite porous material in which one or more other porous layers are laminated on the microporous film or the porous sheet. Quality sheet; and the like.
  • the porous substrate is preferably a microporous membrane from the viewpoint of thinning the separator and strength.
  • a microporous membrane means a membrane that has a large number of micropores inside and has a structure in which these micropores are connected, allowing gas or liquid to pass from one surface to the other. To do.
  • the material for the porous substrate is preferably an electrically insulating material, and may be either an organic material or an inorganic material.
  • the porous substrate contains a thermoplastic resin in order to give the porous substrate a shutdown function.
  • the shutdown function refers to a function of preventing the thermal runaway of the battery by blocking the movement of ions by dissolving the constituent materials and closing the pores of the porous base material when the battery temperature rises.
  • the thermoplastic resin a thermoplastic resin having a melting point of less than 200 ° C. is preferable.
  • the thermoplastic resin include polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; among these, polyolefins are preferable.
  • a microporous membrane containing polyolefin As the porous substrate, a microporous membrane containing polyolefin (referred to as “polyolefin microporous membrane”) is preferable.
  • polyolefin microporous membrane examples include a polyolefin microporous membrane applied to conventional battery separators, and it is preferable to select one having sufficient mechanical properties and ion permeability.
  • the polyolefin microporous membrane preferably contains polyethylene from the viewpoint of exhibiting a shutdown function, and the polyethylene content is preferably 95% by mass or more of the total mass of the polyolefin microporous membrane.
  • the polyolefin microporous membrane is preferably a polyolefin microporous membrane containing polyethylene and polypropylene from the viewpoint of imparting heat resistance that does not easily break when exposed to high temperatures.
  • a polyolefin microporous membrane include a microporous membrane in which polyethylene and polypropylene are mixed in one layer.
  • the microporous membrane preferably contains 95% by mass or more of polyethylene and 5% by mass or less of polypropylene from the viewpoint of achieving both a shutdown function and heat resistance. From the viewpoint of achieving both a shutdown function and heat resistance, a polyolefin microporous membrane having a laminated structure of two or more layers, at least one layer containing polyethylene and at least one layer containing polypropylene is also preferable.
  • the polyolefin contained in the polyolefin microporous membrane is preferably a polyolefin having a weight average molecular weight (Mw) of 100,000 to 5,000,000.
  • Mw weight average molecular weight
  • the Mw of the polyolefin is 100,000 or more, sufficient mechanical properties can be imparted to the microporous membrane.
  • the Mw of the polyolefin is 5 million or less, the shutdown characteristics of the microporous film are good and the microporous film can be easily molded.
  • a melted polyolefin resin is extruded from a T-die to form a sheet, which is crystallized and then stretched, and then heat treated to form a microporous membrane: liquid paraffin, etc.
  • Examples include a method in which a polyolefin resin melted together with a plasticizer is extruded from a T-die, cooled, formed into a sheet, and stretched, and then the plasticizer is extracted and heat-treated to form a microporous film.
  • porous sheets made of fibrous materials include polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; heat-resistant resins such as aromatic polyamide, polyimide, polyethersulfone, polysulfone, polyetherketone, and polyetherimide; cellulose And a porous sheet made of a fibrous material such as non-woven fabric and paper.
  • the heat resistant resin refers to a resin having a melting point of 200 ° C. or higher, or a resin having no melting point and a decomposition temperature of 200 ° C. or higher.
  • Examples of the composite porous sheet include a sheet obtained by laminating a functional layer on a porous sheet made of a microporous film or a fibrous material. Such a composite porous sheet is preferable from the viewpoint of further function addition by the functional layer.
  • Examples of the functional layer include a porous layer made of a heat resistant resin and a porous layer made of a heat resistant resin and an inorganic filler from the viewpoint of imparting heat resistance.
  • Examples of the heat resistant resin include one or more heat resistant resins selected from aromatic polyamide, polyimide, polyethersulfone, polysulfone, polyetherketone and polyetherimide.
  • Examples of the inorganic filler include metal oxides such as alumina; metal hydroxides such as magnesium hydroxide.
  • a method of applying a functional layer to a microporous membrane or a porous sheet a method of bonding the microporous membrane or porous sheet and the functional layer with an adhesive, a microporous membrane or a porous sheet, Examples include a method of thermocompression bonding with the functional layer.
  • the surface of the porous substrate may be subjected to various surface treatments within the range that does not impair the properties of the porous substrate for the purpose of improving the wettability with the coating liquid for forming the porous layer. Good.
  • Examples of the surface treatment include corona treatment, plasma treatment, flame treatment, and ultraviolet irradiation treatment.
  • the thickness of the porous substrate is preferably 5 ⁇ m to 25 ⁇ m from the viewpoint of obtaining good mechanical properties and internal resistance.
  • the Gurley value (JIS P8117: 2009) of the porous substrate is preferably 50 seconds / 100 cc to 200 seconds / 100 cc from the viewpoint of suppressing short circuit of the battery and obtaining sufficient ion permeability.
  • the porosity of the porous substrate is preferably 20% to 60% from the viewpoint of obtaining an appropriate film resistance and shutdown function.
  • the puncture strength of the porous base material is preferably 300 g or more from the viewpoint of improving the separator manufacturing yield and the battery manufacturing yield.
  • the piercing strength of a porous substrate is measured by performing a piercing test using a Kato Tech KES-G5 handy compression tester under the conditions of a radius of curvature of the needle tip of 0.5 mm and a piercing speed of 2 mm / sec. (G).
  • the first porous layer and the second porous layer have a large number of micropores inside, and have a structure in which these micropores are connected. From one surface to the other, a gas or liquid Can pass through.
  • Each of the first porous layer and the second porous layer is a layer provided on the porous substrate as the outermost layer of the separator, and when the separator and the electrode are stacked and pressed or hot pressed, It is a layer to be bonded.
  • the first porous layer is a porous layer containing at least the specific VDF-HFP copolymer (1) provided on one surface of the porous substrate.
  • the first porous layer may further contain a resin other than the specific VDF-HFP copolymer (1), an inorganic filler, an organic filler, and the like.
  • the second porous layer is a porous layer provided on the other surface of the porous substrate and containing at least a polyvinylidene fluoride resin and a resin having a glass transition temperature of 30 ° C. to 120 ° C. .
  • the second porous layer may further contain a resin other than the above, an inorganic filler, an organic filler, and the like.
  • Polyvinylidene fluoride resin includes homopolymers of vinylidene fluoride (ie, polyvinylidene fluoride); copolymers of vinylidene fluoride and other copolymerizable monomers (polyvinylidene fluoride copolymer) And a mixture thereof.
  • Examples of the monomer copolymerizable with vinylidene fluoride include tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, chlorotrifluoroethylene, trichloroethylene, vinyl fluoride, and the like, and one or more of them are used. Can do.
  • the polyvinylidene fluoride resin contained in the second porous layer preferably has a weight average molecular weight (Mw) of 100,000 to 3,000,000.
  • Mw weight average molecular weight
  • the Mw of the polyvinylidene fluoride resin is 100,000 or more, the mechanical properties of the second porous layer are excellent.
  • the Mw of the polyvinylidene fluoride resin is 3 million or less, the viscosity of the coating liquid used for coating molding of the second porous layer does not become too high, and the moldability and crystal formation are good.
  • the porous layer has good porosity.
  • the Mw of the polyvinylidene fluoride resin is more preferably 300,000 to 2,000,000, still more preferably 500,000 to 1,500,000.
  • a VDF-HFP copolymer is preferable from the viewpoint of adhesion to the electrode.
  • By copolymerizing hexafluoropropylene with vinylidene fluoride it is possible to control the crystallinity, heat resistance, resistance to electrolyte solution, and the like of the polyvinylidene fluoride resin to an appropriate range.
  • the content of HFP units is 3% by mass to 20% by mass of the total monomer units, and the weight average molecular weight (Mw) is 100,000-150.
  • Polyvinylidene fluoride-based resin, that is, specific VDF-HFP copolymer (1) is preferable. The reason is the same as the reason for applying the specific VDF-HFP copolymer (1) to the first porous layer.
  • the specific VDF-HFP copolymer (1) may occupy 90% by mass or more of the total amount of the polyvinylidene fluoride resin contained in the second porous layer. Yes, it may occupy 95% by mass or more, and may occupy 100% by mass.
  • the specific VDF-HFP copolymer (1) includes both a copolymer having only VDF units and HFP units, and a copolymer having other monomer units.
  • monomers that form other monomer units include fluorine-containing monomers such as tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, and vinyl fluoride.
  • Monomer units derived from species or two or more species may be contained in the specific VDF-HFP copolymer (1).
  • the specific VDF-HFP copolymer (1) is preferably a binary copolymer having only VDF units and HFP units.
  • the content of HFP units is 3% by mass to 20% by mass of the total monomer units.
  • the HFP unit content in the specific VDF-HFP copolymer (1) is more preferably 5% by mass or more as a lower limit, further preferably 6% by mass or more, and more preferably 18% by mass or less as an upper limit. A mass% or less is more preferable.
  • the specific VDF-HFP copolymer (1) has a weight average molecular weight (Mw) of 100,000 to 1,500,000.
  • Mw weight average molecular weight
  • the lower limit of Mw of the specific VDF-HFP copolymer (1) is more preferably 200,000 or more, further preferably 300,000 or more, further preferably 500,000 or more, and the upper limit is more preferably 1,200,000 or less. One million or less is more preferable.
  • Examples of the method for producing the specific VDF-HFP copolymer (1) include emulsion polymerization and suspension polymerization. It is also possible to select a commercially available VDF-HFP copolymer that satisfies the content of HFP units and the weight average molecular weight.
  • the specific VDF-HFP copolymer (1) may occupy 90% by mass or more of the total amount of all resins contained in the first porous layer, and 95 May occupy 100% by mass or more.
  • Resin having a glass transition temperature of 30 ° C. to 120 ° C. As a resin having a glass transition temperature of 30 ° C. to 120 ° C., from the viewpoint of better adhesion to the electrode by dry heat press, an acrylic resin, vinyl acetate At least one selected from the group consisting of a vinyl resin and a vinyl chloride resin is preferable.
  • an acrylic ester such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, etc. is used alone.
  • Polymerized or copolymerized polymer methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, Polymers obtained by homopolymerizing or copolymerizing methacrylic acid esters such as hydroxypropyl methacrylate and diethylaminoethyl methacrylate; at least one acrylic ester and at least one methacrylate Copolymer with a phosphate ester; a copolymer of at least one selected from acrylic acid esters and methacrylic acid esters and at least one selected from acrylic acid, methacrylic acid, acrylamide, N-methylolacrylamide, diacetone acrylamide, etc. Polymerized copolymer; and the like.
  • PMMA polymethyl methacrylate resin
  • PMMA may be a homopolymer of methyl methacrylate or a copolymer obtained by copolymerizing other monomers other than methyl methacrylate.
  • examples of other monomers to be copolymerized include methyl acrylate, acrylic At least one selected from acids and methacrylic acid is preferred.
  • the weight average molecular weight (Mw) of the acrylic resin is preferably 50,000 to 1,000,000.
  • Mw weight average molecular weight
  • the acrylic resin has an Mw of 50,000 or more, the film-forming property is good and the characteristics of the second porous layer are excellent.
  • the Mw of the acrylic resin is 1,000,000 or less, the viscosity of the coating liquid used for coating molding of the second porous layer does not become too high, and the productivity of the separator is improved.
  • vinyl acetate resin examples include at least one selected from polyvinyl acetate (PVAc), which is a homopolymer of vinyl acetate; vinyl acetate, unsaturated carboxylic acid, olefin, vinyl ether, unsaturated sulfonic acid, and the like. Copolymer with seeds; and the like.
  • PVAc polyvinyl acetate
  • the weight average molecular weight (Mw) of the vinyl acetate resin is preferably 50,000 to 500,000.
  • Mw of the vinyl acetate resin is 50,000 or more, the film-forming property is good and the characteristics of the second porous layer are excellent.
  • Mw of the vinyl acetate resin is 500,000 or less, the viscosity of the coating liquid used for coating molding of the second porous layer does not become too high, and the productivity of the separator is improved.
  • the vinyl chloride resin may be a homopolymer or a copolymer.
  • polyvinyl chloride (PVC) chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer Polymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-anhydrous malein Acid copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer Polymer, vinyl chloride-male
  • the weight average molecular weight (Mw) of the vinyl chloride resin is preferably 5000 to 150,000.
  • Mw of the vinyl chloride resin is 5000 or more, the film-forming property is good and the characteristics of the second porous layer are excellent.
  • Mw of the vinyl chloride resin is 150,000 or less, the viscosity of the coating liquid used for coating molding of the second porous layer does not become too high, and the productivity of the separator is improved.
  • the second porous layer may contain only one kind of resin having a glass transition temperature of 30 ° C. to 120 ° C., or may contain two or more kinds.
  • the content of the resin having a glass transition temperature of 30 ° C. to 120 ° C. in the second porous layer is the second porous layer from the viewpoint of increasing the peel strength between the porous substrate and the second porous layer.
  • 5 mass% or more of the total amount of all the resin contained in a quality layer is preferable, 7 mass% or more is more preferable, 10 mass% or more is further more preferable, 15 mass% or more is still more preferable.
  • the total amount of all resins contained in the second porous layer is preferably 50% by mass or less, more preferably 45% by mass or less, and 40% by mass. The following is more preferable, and 35% by mass or less is more preferable.
  • the form of the polyvinylidene fluoride-based resin and the resin having a glass transition temperature of 30 ° C. to 120 ° C. includes (a) a form in which the former and the latter are compatible; (b) Examples include the form in which the latter is present as a dispersed phase in the former continuous phase; (c) the form in which the latter is dispersed in the form of particles in the former continuous phase;
  • (a) the uniformity of the shape and size of the holes is increased, and the adhesion points to the electrode are scattered with high uniformity on the surface of the second porous layer, and the adhesion to the electrode is excellent.
  • (A), (b) and (c) can be confirmed by observing the cross section of the second porous layer with an electron microscope.
  • the total of the polyvinylidene fluoride resin and the resin having a glass transition temperature of 30 ° C. to 120 ° C. is the total amount of all the resins contained in the second porous layer. It may occupy 90% by mass or more, may occupy 95% by mass or more, and may occupy 100% by mass.
  • the 1st porous layer may contain other resins other than specific VDF-HFP copolymer (1).
  • the second porous layer may contain a resin other than the polyvinylidene fluoride resin and a resin having a glass transition temperature of 30 ° C. to 120 ° C.
  • Examples of the resin that may be contained in the first porous layer or the second porous layer include a fluorine-based rubber, a styrene-butadiene copolymer, a homopolymer of a vinyl nitrile compound (acrylonitrile, methacrylonitrile, etc.) Examples thereof include copolymers, carboxymethyl cellulose, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, and polyethers (polyethylene oxide, polypropylene oxide, etc.).
  • the 1st porous layer or the 2nd porous layer may contain the filler which consists of an inorganic substance or an organic substance in order to improve the slipperiness and heat resistance of a separator. In that case, it is preferable to make it content and particle size of the grade which does not disturb the effect of the first form.
  • the filler is preferably an inorganic filler from the viewpoint of improving cell strength and ensuring battery safety.
  • the average particle diameter of the filler is preferably 0.01 ⁇ m to 5 ⁇ m.
  • the lower limit is more preferably 0.1 ⁇ m or more, and the upper limit is more preferably 1 ⁇ m or less.
  • an inorganic filler that is stable with respect to the electrolytic solution and electrochemically stable is preferable.
  • metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, chromium hydroxide, zirconium hydroxide, cerium hydroxide, nickel hydroxide, boron hydroxide; alumina, titania, magnesia, Metal oxides such as silica, zirconia, and barium titanate; carbonates such as calcium carbonate and magnesium carbonate; sulfates such as barium sulfate and calcium sulfate; clay minerals such as calcium silicate and talc; These inorganic fillers may be used alone or in combination of two or more.
  • the inorganic filler may be surface-modified with a silane coupling agent or the like.
  • the inorganic filler is preferably at least one of a metal hydroxide and a metal oxide from the viewpoint of ensuring the stability in the battery and the safety of the battery, and from the viewpoint of imparting flame retardancy and neutralizing effect, metal hydroxide Products are preferred, and magnesium hydroxide is more preferred.
  • the particle shape of the inorganic filler is not limited, and may be a shape close to a sphere or a plate shape, but from the viewpoint of suppressing short circuit of the battery, it should be a plate-like particle or a non-aggregated primary particle. Is preferred.
  • the content of the inorganic filler in the first porous layer or the second porous layer is included in each porous layer. 5% by mass to 75% by mass of the total amount of the total resin and the inorganic filler is preferred.
  • the content of the inorganic filler is 5% by mass or more, thermal contraction of the separator is suppressed when heat is applied, which is preferable from the viewpoint of dimensional stability. From this viewpoint, the content of the inorganic filler is more preferably 10% by mass or more, and further preferably 20% by mass or more.
  • the content of the inorganic filler is 75% by mass or less, it is preferable from the viewpoint of ensuring adhesion of the porous layer to the electrode. From this viewpoint, the content of the inorganic filler is more preferably 70% by mass or less, and further preferably 65% by mass or less.
  • organic filler examples include cross-linked acrylic resins such as cross-linked polymethyl methacrylate, cross-linked polystyrene, and the like, and cross-linked polymethyl methacrylate is preferable.
  • the 1st porous layer and the 2nd porous layer may contain additives, such as dispersing agents, such as surfactant, a wetting agent, an antifoamer, and a pH adjuster.
  • the dispersant is added to a coating solution used for coating and forming the porous layer for the purpose of improving dispersibility, coating properties, and storage stability.
  • Wetting agents, antifoaming agents, and pH adjusters are used in coating liquids used for coating and forming porous layers, for example, for the purpose of improving familiarity with porous substrates, and for entraining air in the coating liquid. It is added for the purpose of suppressing or adjusting the pH.
  • the thickness of the porous layer is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more from the viewpoint of adhesion to the electrode on one side of the porous substrate, and from the viewpoint of the energy density of the battery, 8. 0 ⁇ m or less is preferable, and 6.0 ⁇ m or less is more preferable.
  • the difference between the thickness of the first porous layer and the thickness of the second porous layer is preferably 20% or less of the total thickness of both surfaces, and the lower the better.
  • the weight of the porous layer is preferably 0.5 g / m 2 or more, more preferably 0.75 g / m 2 or more, from the viewpoint of adhesion to the electrode on one side of the porous substrate, and an ion permeability viewpoint. Therefore, 5.0 g / m 2 or less is preferable, and 4.0 g / m 2 or less is more preferable.
  • the porosity of the porous layer is preferably 30% or more from the viewpoint of ion permeability, preferably 80% or less, more preferably 60% or less from the viewpoint of mechanical strength.
  • the method for obtaining the porosity of the porous layer in the first embodiment is the same as the method for obtaining the porosity of the porous substrate.
  • the average pore diameter of the porous layer is preferably 10 nm or more from the viewpoint of ion permeability, and preferably 200 nm or less from the viewpoint of adhesiveness with the electrode.
  • the average pore diameter of the porous layer in the first embodiment is calculated by the following formula, assuming that all the pores are cylindrical.
  • d represents the average pore diameter (diameter) of the porous layer
  • V represents the pore volume per 1 m 2 of the porous layer
  • S represents the pore surface area per 1 m 2 of the porous layer.
  • the pore volume V per 1 m 2 of the porous layer is calculated from the porosity of the porous layer.
  • the pore surface area S per 1 m 2 of the porous layer is determined by the following method. First, a specific surface area of the porous substrate (m 2 / g) and specific surface area of the separator (m 2 / g), by applying the BET equation to the nitrogen gas adsorption method, is calculated from the nitrogen gas adsorption. The specific surface area (m 2 / g) is multiplied by the basis weight (g / m 2 ) to calculate the pore surface area per 1 m 2 . Then, by subtracting the pore surface area of the porous substrate 1 m 2 per the pore surface area per separator 1 m 2, to calculate the pore surface area S per porous layer 1 m 2.
  • the peel strength between the porous substrate and the porous layer is preferably 0.20 N / 10 mm or more.
  • the peel strength is more preferably 0.30 N / 10 mm or more, and the higher the better.
  • the upper limit of the peel strength is not limited, but is usually 2.0 N / 10 mm or less.
  • the thickness of the first form separator is preferably 5 ⁇ m or more from the viewpoint of mechanical strength, and preferably 35 ⁇ m or less from the viewpoint of the energy density of the battery.
  • the puncture strength of the first form separator is preferably 250 to 1000 g, more preferably 300 to 600 g.
  • the method for measuring the puncture strength of the separator is the same as the method for measuring the puncture strength of the porous substrate.
  • the porosity of the separator of the first form is preferably 30% to 65%, more preferably 30% to 60% from the viewpoints of adhesion to electrodes, handling properties, ion permeability, and mechanical strength.
  • the Gurley value (JIS P8117: 2009) of the separator of the first form is preferably 100 seconds / 100 cc to 300 seconds / 100 cc from the viewpoint of mechanical strength and battery load characteristics.
  • the separator of the first form can be produced, for example, by a wet coating method having the following steps (i) to (iv).
  • a second coating liquid containing a polyvinylidene fluoride resin and a resin having a glass transition temperature of 30 ° C. to 120 ° C. is applied to the other surface of the porous substrate to form a second coating layer.
  • Process. (Iii) The porous base material on which the first coating layer and the second coating layer are formed is immersed in a coagulating liquid, and the resin is solidified while inducing phase separation in the first coating layer and the second coating layer. The process of forming a 1st porous layer and a 2nd porous layer on a porous base material, and obtaining a composite film.
  • coating liquid when the matters common to the first coating liquid and the second coating liquid are described, both are collectively referred to as “coating liquid” and are common to the first coating layer and the second coating layer.
  • coating layer when explaining matters to be performed, both are collectively referred to as “coating layer”, and when explaining matters common to the first porous layer and the second porous layer, both are collectively referred to as “porous layer”.
  • the coating solution is prepared by dissolving or dispersing polyvinylidene fluoride resin and other resins in a solvent.
  • the filler is contained in the porous layer, the filler is dispersed in each coating solution.
  • the solvent used for preparing the coating solution includes a solvent that dissolves the polyvinylidene fluoride resin (hereinafter, also referred to as “good solvent”).
  • good solvent include polar amide solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, and dimethylformamide.
  • the solvent used for preparing the coating liquid preferably contains a phase separation agent that induces phase separation from the viewpoint of forming a porous layer having a good porous structure. Therefore, the solvent used for preparing the coating liquid is preferably a mixed solvent of a good solvent and a phase separation agent.
  • the phase separation agent is preferably mixed with a good solvent in an amount within a range that can ensure a viscosity suitable for coating. Examples of the phase separation agent include water, methanol, ethanol, propyl alcohol, butyl alcohol, butanediol, ethylene glycol, propylene glycol, and tripropylene glycol.
  • the solvent used for the preparation of the coating liquid is a mixed solvent of a good solvent and a phase separation agent from the viewpoint of forming a good porous structure, including 60% by mass or more of the good solvent, and 40% of the phase separation agent. % Is preferable.
  • the resin concentration of the coating solution is preferably 1% by mass to 20% by mass from the viewpoint of forming a good porous structure.
  • Examples of means for applying the coating liquid to the porous substrate include a Mayer bar, a die coater, a reverse roll coater, and a gravure coater. From the viewpoint of productivity, it is preferable to apply the first coating liquid and the second coating liquid to the porous substrate at the same time.
  • the coagulation liquid generally contains a good solvent and a phase separation agent used for preparing the coating liquid, and water. It is preferable in production that the mixing ratio of the good solvent and the phase separation agent is matched to the mixing ratio of the mixed solvent used for preparing the coating liquid.
  • the content of water in the coagulation liquid is preferably 40% by mass to 90% by mass from the viewpoint of formation of a porous structure and productivity.
  • the temperature of the coagulation liquid is, for example, 20 ° C. to 50 ° C.
  • the separator of the first form can also be manufactured by a dry coating method.
  • the dry coating method is a method in which a coating liquid containing a resin is applied to a porous substrate to form a coating layer, and then the coating layer is dried to solidify the coating layer. This is a method of forming a porous layer.
  • the wet coating method is preferable from the viewpoint of obtaining a good porous structure.
  • the separator of the first form can also be produced by a method in which a porous layer is produced as an independent sheet, and this porous layer is stacked on a porous substrate and laminated by thermocompression bonding or an adhesive.
  • a method for producing the porous layer as an independent sheet include a method in which the wet coating method or the dry coating method described above is applied to form a porous layer on the release sheet, and the release sheet is peeled off from the porous layer. It is done.
  • the non-aqueous secondary battery separator of the second form (also referred to as “second form of separator”) includes a porous substrate and an adhesive porous layer provided on one or both sides of the porous substrate. Prepare.
  • the adhesive porous layer has a vinylidene fluoride monomer unit and a hexafluoropropylene monomer unit, and the content of the hexafluoropropylene monomer unit is 5 of all monomer units.
  • a polyvinylidene fluoride resin having a mass average molecular weight of 100,000 to 1,500,000 and a glass transition temperature of 30 ° C. to 120 ° C.
  • the adhesive porous layer may be present only on one side of the porous substrate or on both sides of the porous substrate. When the adhesive porous layer is present only on one surface of the porous substrate, the other surface of the porous substrate may not have a layer and may have another layer.
  • VDF unit a vinylidene fluoride monomer unit
  • HFP unit a hexafluoropropylene monomer unit
  • HFP-HFP co-polymer a polyvinylidene fluoride resin having a VDF unit and an HFP unit
  • VDF-HFP co-polymer A VDF-HFP copolymer having a content of HFP units of 5% to 20% by mass of all monomer units and a weight average molecular weight of 100,000 to 1,500,000 is also referred to as “specific VDF- Also referred to as “HFP copolymer (2)”.
  • the adhesive porous layer is an outermost layer of the separator and is a layer that adheres to the electrode.
  • the separator of the second form comprises an adhesive porous layer containing a specific VDF-HFP copolymer (2) and a resin having a glass transition temperature of 30 ° C. to 120 ° C. Excellent adhesion. This mechanism is not necessarily clear, but is presumed as follows.
  • a VDF-HFP copolymer is preferable from the viewpoint of adhesion to electrodes.
  • the separator of the second form is a specific VDF in which the content of HFP units is 5% by mass to 20% by mass of the total monomer units and the weight average molecular weight (Mw) is 100,000 to 1.5 million for the following reasons.
  • -The HFP copolymer (2) is included in the adhesive porous layer.
  • the HFP unit content of the VDF-HFP copolymer is 5% by mass or more, the polymer chain has high mobility when dry heat pressing is performed, and the polymer chain enters the irregularities on the electrode surface, thereby exhibiting an anchor effect. And improving the adhesion of the adhesive porous layer to the electrode. From this viewpoint, the HFP unit content of the VDF-HFP copolymer is 5% by mass or more, more preferably 5.5% by mass or more, and further preferably 6% by mass or more.
  • the HFP unit content of the VDF-HFP copolymer is 20% by mass or less, it is difficult to dissolve in the electrolyte solution and does not swell excessively, so that adhesion between the electrode and the adhesive porous layer is maintained inside the battery. Be drunk. From this viewpoint, the HFP unit content of the VDF-HFP copolymer is 20% by mass or less, more preferably 18% by mass or less, and further preferably 15% by mass or less.
  • the adhesive porous layer can secure the mechanical properties that can withstand the adhesion treatment with the electrode, and the adhesion with the electrode is good. Further, if the Mw of the VDF-HFP copolymer is 100,000 or more, it is difficult to dissolve in the electrolytic solution, so that the adhesion between the electrode and the adhesive porous layer is maintained inside the battery. From these viewpoints, the MDF of the VDF-HFP copolymer is 100,000 or more, more preferably 200,000 or more, further preferably 300,000 or more, and further preferably 500,000 or more.
  • the Mw of the VDF-HFP copolymer When the Mw of the VDF-HFP copolymer is 1.5 million or less, the viscosity of the coating liquid used for coating and forming the adhesive porous layer is not too high, and the moldability and crystal formation are good. The uniformity of the surface properties of the layer is high, and as a result, the adhesion of the adhesive porous layer to the electrode is good.
  • the Mw of the VDF-HFP copolymer is 1,500,000 or less, the polymer chain has high mobility when dry heat pressing is performed, the polymer chain enters the irregularities of the electrode surface, and an anchor effect is exhibited. Improve adhesion of the adhesive porous layer to the electrode. From these viewpoints, the Mw of the VDF-HFP copolymer is 1.5 million or less, more preferably 1.2 million or less, and still more preferably 1 million or less.
  • the resin having a glass transition temperature of 30 ° C. to 120 ° C. contained in the adhesive porous layer enhances the fluidity of the adhesive porous layer during dry heat pressing.
  • a polymer chain enters the unevenness of the electrode surface to develop an anchor effect and improve the adhesion of the adhesive porous layer to the electrode.
  • the glass transition temperature of the resin having a glass transition temperature of 30 ° C. to 120 ° C. is 120 ° C. or less, more preferably 115 ° C. or less, more preferably 110 ° C. or less, from the viewpoint of developing fluidity by heat application of a dry heat press. More preferably, from the viewpoint of ensuring the heat resistance of the adhesive porous layer, it is 30 ° C. or higher, more preferably 35 ° C. or higher, and still more preferably 40 ° C. or higher.
  • the separator of the second form is excellent in adhesion with the electrode by dry heat press, it is difficult to be displaced from the electrode in the battery manufacturing process, and the manufacturing yield of the battery is improved.
  • the second form of the separator improves the cycle characteristics (capacity retention rate) of the battery because it is excellent in adhesion to the electrode by dry heat press.
  • porous substrate The porous substrate in the second form is synonymous with the porous substrate in the first form.
  • the specific form and preferred form of the porous substrate in the second form are the same as the specific form and preferred form of the porous base in the first form.
  • the adhesive porous layer is a layer that is provided on one or both sides of the porous substrate as the outermost layer of the separator and adheres to the electrode when the separator and the electrode are stacked and pressed or hot pressed.
  • the adhesive porous layer has a large number of micropores inside and has a structure in which these micropores are connected, and gas or liquid can pass from one surface to the other. It has become.
  • the adhesive porous layer comprises at least the specific VDF-HFP copolymer (2) and a resin having a glass transition temperature of 30 ° C. to 120 ° C. provided on one or both sides of the porous substrate. It is a porous layer to contain.
  • the adhesive porous layer may further contain a resin other than the above, an inorganic filler, an organic filler, and the like.
  • the adhesive porous layer is preferably on both sides rather than only on one side of the porous substrate from the viewpoint of excellent battery cycle characteristics. This is because when the adhesive porous layer is on both sides of the porous substrate, both sides of the separator are well adhered to both electrodes via the adhesive porous layer.
  • the specific VDF-HFP copolymer (2) includes both a copolymer having only VDF units and HFP units, and a copolymer having other monomer units.
  • monomers that form other monomer units include fluorine-containing monomers such as tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, and vinyl fluoride.
  • Monomer units derived from species or two or more species may be contained in the specific VDF-HFP copolymer (2).
  • the specific VDF-HFP copolymer (2) is preferably a binary copolymer having only VDF units and HFP units.
  • the content of HFP units is 5% by mass to 20% by mass of the total monomer units.
  • the lower limit of the HFP unit content in the specific VDF-HFP copolymer (2) is more preferably 5.5% by mass or more, still more preferably 6% by mass or more, and the upper limit is more preferably 18% by mass or less. 15% by mass or less is more preferable.
  • the specific VDF-HFP copolymer (2) has a weight average molecular weight (Mw) of 100,000 to 1,500,000.
  • Mw weight average molecular weight
  • the lower limit of Mw of the specific VDF-HFP copolymer (2) is more preferably 200,000 or more, further preferably 300,000 or more, further preferably 500,000 or more, and the upper limit is more preferably 1,200,000 or less. One million or less is more preferable.
  • Examples of the method for producing the specific VDF-HFP copolymer (2) include emulsion polymerization and suspension polymerization. It is also possible to select a commercially available VDF-HFP copolymer that satisfies the content of HFP units and the weight average molecular weight.
  • the lower limit of the content of the specific VDF-HFP copolymer (2) in the adhesive porous layer is preferably 50% by mass or more based on the total amount of all resins contained in the adhesive porous layer, and 55% by mass. % Or more, more preferably 60% by weight or more, still more preferably 65% by weight or more, and the upper limit is preferably 95% by weight or less, more preferably 93% by weight or less, still more preferably 90% by weight or less, 85 A mass% or less is more preferable.
  • Resin having a glass transition temperature of 30 ° C. to 120 ° C. As a resin having a glass transition temperature of 30 ° C. to 120 ° C., from the viewpoint of better adhesion to the electrode by dry heat press, an acrylic resin, vinyl acetate At least one selected from the group consisting of a vinyl resin and a vinyl chloride resin is preferable.
  • an acrylic ester such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, etc. is used alone.
  • Polymerized or copolymerized polymer methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, Polymers obtained by homopolymerizing or copolymerizing methacrylic acid esters such as hydroxypropyl methacrylate and diethylaminoethyl methacrylate; at least one acrylic ester and at least one methacrylate Copolymer with a phosphate ester; a copolymer of at least one selected from acrylic acid esters and methacrylic acid esters and at least one selected from acrylic acid, methacrylic acid, acrylamide, N-methylolacrylamide, diacetone acrylamide, etc. Polymerized copolymer; and the like.
  • PMMA polymethyl methacrylate resin
  • PMMA may be a homopolymer of methyl methacrylate or a copolymer obtained by copolymerizing other monomers other than methyl methacrylate.
  • examples of other monomers to be copolymerized include methyl acrylate, acrylic At least one selected from acids and methacrylic acid is preferred.
  • the weight average molecular weight (Mw) of the acrylic resin is preferably 50,000 to 1,000,000.
  • Mw weight average molecular weight
  • the acrylic resin has an Mw of 50,000 or more, the film-forming property is good and the properties of the adhesive porous layer are excellent.
  • the Mw of the acrylic resin is 1,000,000 or less, the viscosity of the coating liquid used for coating molding of the adhesive porous layer does not become too high, and the productivity of the separator is improved.
  • vinyl acetate resin examples include at least one selected from polyvinyl acetate (PVAc), which is a homopolymer of vinyl acetate; vinyl acetate, unsaturated carboxylic acid, olefin, vinyl ether, unsaturated sulfonic acid, and the like. Copolymer with seeds; and the like.
  • PVAc polyvinyl acetate
  • the weight average molecular weight (Mw) of the vinyl acetate resin is preferably 50,000 to 500,000.
  • Mw of the vinyl acetate resin is 50,000 or more, the film-forming property is good and the properties of the adhesive porous layer are excellent.
  • Mw of the vinyl acetate resin is 500,000 or less, the viscosity of the coating liquid used for coating molding of the adhesive porous layer does not become too high, and the productivity of the separator is improved.
  • the vinyl chloride resin may be a homopolymer or a copolymer.
  • polyvinyl chloride (PVC) chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer Polymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-anhydrous malein Acid copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer Polymer, vinyl chloride-male
  • the weight average molecular weight (Mw) of the vinyl chloride resin is preferably 5000 to 150,000.
  • Mw of the vinyl chloride resin is 5000 or more, the film-forming property is good and the properties of the adhesive porous layer are excellent.
  • Mw of the vinyl chloride resin is 150,000 or less, the viscosity of the coating liquid used for coating molding of the adhesive porous layer does not become too high, and the productivity of the separator is improved.
  • the adhesive porous layer may contain only one kind of resin having a glass transition temperature of 30 ° C. to 120 ° C., or may contain two or more kinds.
  • the content of the resin having a glass transition temperature of 30 ° C. to 120 ° C. in the adhesive porous layer is not limited to the adhesive porous layer from the viewpoint of increasing the peel strength between the porous substrate and the adhesive porous layer. 5 mass% or more of the total amount of all resins contained is preferable, 7 mass% or more is more preferable, 10 mass% or more is further more preferable, and 15 mass% or more is still more preferable. On the other hand, from the viewpoint of suppressing cohesive failure of the adhesive porous layer, 50% by mass or less of the total amount of all resins contained in the adhesive porous layer is preferable, 45% by mass or less is more preferable, and 40% by mass or less is more preferable. Preferably, 35 mass% or less is more preferable.
  • the specific VDF-HFP copolymer (2) and the resin having a glass transition temperature of 30 ° C. to 120 ° C. include (a) a form in which the former and the latter are compatible (B) a form in which the latter is present as a dispersed phase in the former continuous phase; (c) a form in which the latter is dispersed in the form of particles in the former continuous phase; preferable.
  • (a) the uniformity of the shape and size of the holes is increased, and the adhesion points with respect to the electrodes are scattered with high uniformity on the surface of the adhesive porous layer, and the adhesion to the electrodes is excellent.
  • (A), (b) and (c) can be confirmed by observing the cross section of the adhesive porous layer with an electron microscope.
  • the total resin including the specific VDF-HFP copolymer (2) and the resin having a glass transition temperature of 30 ° C. to 120 ° C. is included in the adhesive porous layer. May occupy 90% by mass or more of the total amount, may occupy 95% by mass or more, and may occupy 100% by mass.
  • the adhesive porous layer may contain other resin other than the specific VDF-HFP copolymer (2) and a resin having a glass transition temperature of 30 ° C. to 120 ° C.
  • Examples of the polyvinylidene fluoride resin other than the specific VDF-HFP copolymer (2) include, for example, a VDF-HFP copolymer in which the content of HFP units is different from that of the specific VDF-HFP copolymer (2); And a homopolymer of vinylidene (that is, polyvinylidene fluoride); a copolymer of vinylidene fluoride and at least one selected from tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, vinyl fluoride, and the like.
  • Resins other than polyvinylidene fluoride resins include fluorine rubber, styrene-butadiene copolymers, homopolymers or copolymers of vinyl nitrile compounds (acrylonitrile, methacrylonitrile, etc.), carboxymethyl cellulose, hydroxyalkyl cellulose , Polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, polyether (polyethylene oxide, polypropylene oxide, etc.) and the like.
  • the adhesive porous layer may contain a filler made of an inorganic material or an organic material for the purpose of improving the slipperiness and heat resistance of the separator. In that case, it is preferable to set it as content and particle
  • the filler is preferably an inorganic filler from the viewpoint of improving cell strength and ensuring battery safety.
  • the average particle diameter of the filler is preferably 0.01 ⁇ m to 5 ⁇ m.
  • the lower limit is more preferably 0.1 ⁇ m or more, and the upper limit is more preferably 1 ⁇ m or less.
  • an inorganic filler that is stable with respect to the electrolytic solution and electrochemically stable is preferable.
  • metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, chromium hydroxide, zirconium hydroxide, cerium hydroxide, nickel hydroxide, boron hydroxide; alumina, titania, magnesia, Metal oxides such as silica, zirconia, and barium titanate; carbonates such as calcium carbonate and magnesium carbonate; sulfates such as barium sulfate and calcium sulfate; clay minerals such as calcium silicate and talc; These inorganic fillers may be used alone or in combination of two or more.
  • the inorganic filler may be surface-modified with a silane coupling agent or the like.
  • the inorganic filler is preferably at least one of a metal hydroxide and a metal oxide from the viewpoint of ensuring the stability in the battery and the safety of the battery, and from the viewpoint of imparting flame retardancy and neutralizing effect, metal hydroxide Products are preferred, and magnesium hydroxide is more preferred.
  • the particle shape of the inorganic filler is not limited, and may be a shape close to a sphere or a plate shape, but from the viewpoint of suppressing short circuit of the battery, it should be a plate-like particle or a non-aggregated primary particle. Is preferred.
  • the content of the inorganic filler in the adhesive porous layer is 5% by mass to 75% of the total amount of all resins and inorganic fillers contained in the adhesive porous layer. Mass% is preferred.
  • the content of the inorganic filler is 5% by mass or more, thermal contraction of the separator is suppressed when heat is applied, which is preferable from the viewpoint of dimensional stability.
  • the content of the inorganic filler is more preferably 10% by mass or more, and further preferably 20% by mass or more.
  • the content of the inorganic filler is preferably 75% by mass or less from the viewpoint of ensuring adhesion of the adhesive porous layer to the electrode. From this viewpoint, the content of the inorganic filler is more preferably 70% by mass or less, and further preferably 65% by mass or less.
  • organic filler examples include cross-linked acrylic resins such as cross-linked polymethyl methacrylate, cross-linked polystyrene, and the like, and cross-linked polymethyl methacrylate is preferable.
  • the adhesive porous layer may contain additives such as a dispersant such as a surfactant, a wetting agent, an antifoaming agent, and a pH adjusting agent.
  • a dispersant such as a surfactant, a wetting agent, an antifoaming agent, and a pH adjusting agent.
  • the dispersant is added to a coating solution used for coating and forming the adhesive porous layer for the purpose of improving dispersibility, coating properties, and storage stability.
  • Wetting agents, antifoaming agents, and pH adjusters are used in coating liquids used for coating and forming porous adhesive layers, for example, to improve compatibility with porous substrates. It is added for the purpose of suppressing the loading or for the purpose of adjusting the pH.
  • the thickness of the adhesive porous layer is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more from the viewpoint of adhesion to the electrode on one side of the porous substrate, and from the viewpoint of battery energy density, 8.0 ⁇ m or less is preferable, and 6.0 ⁇ m or less is more preferable.
  • the difference between the thickness of the adhesive porous layer on one surface and the thickness of the adhesive porous layer on the other surface is the sum of both surfaces It is preferable that it is 20% or less of the thickness of this, and it is so preferable that it is low.
  • the weight of the adhesive porous layer is preferably 0.5 g / m 2 or more, more preferably 0.75 g / m 2 or more, from the viewpoint of adhesion to the electrode on one side of the porous substrate, and ion permeability.
  • 5.0 g / m 2 or less is preferable, and 4.0 g / m 2 or less is more preferable.
  • the porosity of the adhesive porous layer is preferably 30% or more from the viewpoint of ion permeability, preferably 80% or less, more preferably 60% or less from the viewpoint of mechanical strength.
  • the method for obtaining the porosity of the adhesive porous layer in the second embodiment is the same as the method for obtaining the porosity of the porous substrate.
  • the average pore diameter of the adhesive porous layer is preferably 10 nm or more from the viewpoint of ion permeability, and 200 nm or less is preferable from the viewpoint of adhesion to the electrode.
  • the peel strength between the porous substrate and the adhesive porous layer is preferably 0.20 N / 10 mm or more.
  • the peel strength is 0.20 N / 10 mm or more, the separator is easily handled in the battery manufacturing process. From this viewpoint, the peel strength is more preferably 0.30 N / 10 mm or more, and the higher the better.
  • the upper limit of the peel strength is not limited, but is usually 2.0 N / 10 mm or less.
  • the thickness of the second form separator is preferably 5 ⁇ m or more from the viewpoint of mechanical strength, and is preferably 35 ⁇ m or less from the viewpoint of the energy density of the battery.
  • the pin puncture strength of the second form separator is preferably 250 g to 1000 g, more preferably 300 g to 600 g.
  • the method for measuring the puncture strength of the separator is the same as the method for measuring the puncture strength of the porous substrate.
  • the porosity of the separator of the second form is preferably 30% to 65%, more preferably 30% to 60% from the viewpoints of adhesion to the electrode, handling properties, ion permeability, and mechanical strength.
  • the Gurley value (JIS P8117: 2009) of the separator of the second form is preferably 100 seconds / 100 cc to 300 seconds / 100 cc from the viewpoint of mechanical strength and battery load characteristics.
  • the separator of the second form can be produced, for example, by a wet coating method having the following steps (i) to (iii).
  • the porous base material on which the coating layer is formed is immersed in a coagulation liquid, and the polyvinylidene fluoride resin is solidified while inducing phase separation in the coating layer, thereby forming the porous layer on the porous base material. And obtaining a composite membrane.
  • the coating solution is prepared by dissolving or dispersing a polyvinylidene fluoride resin and a resin having a glass transition temperature of 30 ° C. to 120 ° C. in a solvent.
  • the filler is contained in the adhesive porous layer, the filler is dispersed in the coating liquid.
  • the solvent used for preparing the coating solution includes a solvent that dissolves the polyvinylidene fluoride resin (hereinafter, also referred to as “good solvent”).
  • good solvent include polar amide solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, and dimethylformamide.
  • the solvent used for preparing the coating liquid preferably contains a phase separation agent that induces phase separation from the viewpoint of forming a porous layer having a good porous structure. Therefore, the solvent used for preparing the coating liquid is preferably a mixed solvent of a good solvent and a phase separation agent.
  • the phase separation agent is preferably mixed with a good solvent in an amount within a range that can ensure a viscosity suitable for coating. Examples of the phase separation agent include water, methanol, ethanol, propyl alcohol, butyl alcohol, butanediol, ethylene glycol, propylene glycol, and tripropylene glycol.
  • the solvent used for the preparation of the coating liquid is a mixed solvent of a good solvent and a phase separation agent from the viewpoint of forming a good porous structure, including 60% by mass or more of the good solvent, and 40% of the phase separation agent. % Is preferable.
  • the resin concentration of the coating solution is preferably 1% by mass to 20% by mass from the viewpoint of forming a good porous structure.
  • Examples of means for applying the coating liquid to the porous substrate include a Mayer bar, a die coater, a reverse roll coater, and a gravure coater.
  • a coating liquid When forming a porous layer on both surfaces of a porous base material, it is preferable from a viewpoint of productivity to apply a coating liquid to a base material simultaneously on both surfaces.
  • the coagulation liquid generally contains a good solvent and a phase separation agent used for preparing the coating liquid, and water. It is preferable in production that the mixing ratio of the good solvent and the phase separation agent is matched to the mixing ratio of the mixed solvent used for preparing the coating liquid.
  • the content of water in the coagulation liquid is preferably 40% by mass to 90% by mass from the viewpoint of formation of a porous structure and productivity.
  • the temperature of the coagulation liquid is, for example, 20 ° C. to 50 ° C.
  • the second type separator can also be manufactured by a dry coating method.
  • the dry coating method is a method in which a coating liquid containing a resin is applied to a porous substrate to form a coating layer, and then the coating layer is dried to solidify the coating layer. This is a method of forming a porous layer.
  • the wet coating method is preferable from the viewpoint of obtaining a good porous structure.
  • the separator of the second form can also be produced by a method in which a porous layer is produced as an independent sheet, and this porous layer is stacked on a porous substrate and laminated by thermocompression bonding or an adhesive.
  • a method for producing the porous layer as an independent sheet include a method in which the wet coating method or the dry coating method described above is applied to form a porous layer on the release sheet, and the release sheet is peeled off from the porous layer. It is done.
  • the non-aqueous secondary battery of the present disclosure is a non-aqueous secondary battery that obtains an electromotive force by doping or dedoping lithium, and includes a positive electrode, a negative electrode, and a separator for the non-aqueous secondary battery of the present disclosure.
  • Doping means occlusion, loading, adsorption, or insertion, and means a phenomenon in which lithium ions enter an active material of an electrode such as a positive electrode.
  • the non-aqueous secondary battery of the present disclosure has, for example, a structure in which a battery element in which a negative electrode and a positive electrode are opposed to each other with a separator enclosed in an exterior material together with an electrolytic solution.
  • the nonaqueous secondary battery of the present disclosure is suitable for a nonaqueous electrolyte secondary battery, particularly a lithium ion secondary battery.
  • the non-aqueous secondary battery provided with the first form separator has a high production yield because the first form separator is excellent in adhesion between the positive electrode and the negative electrode by dry heat press.
  • the non-aqueous secondary battery provided with the first type separator is excellent in the cycle characteristics (capacity maintenance ratio) of the battery because the first type separator is excellent in adhesion between the positive electrode and the negative electrode by dry heat press.
  • the non-aqueous secondary battery provided with the second type separator has a high production yield because the second type separator is excellent in adhesion to an electrode by dry heat press.
  • the non-aqueous secondary battery provided with the second type separator is excellent in the cycle characteristics (capacity maintenance ratio) of the battery because the second type separator is excellent in adhesion to the electrode by dry heat press.
  • the positive electrode there is a structure in which an active material layer including a positive electrode active material and a binder resin is disposed on a current collector.
  • the active material layer may further contain a conductive additive.
  • the positive electrode active material include lithium-containing transition metal oxides. Specifically, LiCoO 2 , LiNiO 2 , LiMn 1/2 Ni 1/2 O 2 , LiCo 1/3 Mn 1/3 Ni 1 / 3 O 2, LiMn 2 O 4 , LiFePO 4, LiCo 1/2 Ni 1/2 O 2, LiAl 1/4 Ni 3/4 O 2 and the like.
  • the binder resin include polyvinylidene fluoride resins and styrene-butadiene copolymers.
  • the conductive aid include carbon materials such as acetylene black, ketjen black, and graphite powder.
  • the current collector include aluminum foil, titanium foil, and stainless steel foil having a thickness of 5 ⁇ m to 20 ⁇ m.
  • the polyvinylidene fluoride resin contained in the porous layer of the first type separator is excellent in oxidation resistance. It is easy to apply LiMn 1/2 Ni 1/2 O 2 , LiCo 1/3 Mn 1/3 Ni 1/3 O 2, etc. that can be operated at a high voltage.
  • the polyvinylidene fluoride resin contained in the adhesive porous layer of the separator of the second form is excellent in oxidation resistance.
  • LiMn 1/2 Ni 1/2 O 2 , LiCo 1/3 Mn 1/3 Ni 1 that can be operated at a high voltage of 4.2 V or more as a positive electrode active material by being arranged on the positive electrode side of the water-based secondary battery. / 3 O 2 etc. are easy to apply.
  • Examples of embodiments of the negative electrode include a structure in which an active material layer including a negative electrode active material and a binder resin is disposed on a current collector.
  • the active material layer may further contain a conductive additive.
  • Examples of the negative electrode active material include materials that can occlude lithium electrochemically, and specific examples include carbon materials; alloys of silicon, tin, aluminum, and the like with lithium; wood alloys.
  • Examples of the binder resin include polyvinylidene fluoride resins and styrene-butadiene copolymers.
  • Examples of the conductive aid include carbon materials such as acetylene black, ketjen black, and graphite powder.
  • Examples of the current collector include copper foil, nickel foil, and stainless steel foil having a thickness of 5 ⁇ m to 20 ⁇ m. Moreover, it may replace with said negative electrode and may use metal lithium foil as a negative electrode.
  • the electrolytic solution is a solution in which a lithium salt is dissolved in a non-aqueous solvent.
  • the lithium salt include LiPF 6 , LiBF 4 , LiClO 4, and the like.
  • the non-aqueous solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, and vinylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, and fluorine-substituted products thereof; and cyclic esters such as ⁇ -butyrolactone and ⁇ -valerolactone. These may be used alone or in combination.
  • cyclic carbonate and chain carbonate were mixed at a mass ratio (cyclic carbonate: chain carbonate) of 20:80 to 40:60, and lithium salt was dissolved in 0.5 mol / L to 1.5 mol / L.
  • a solution is preferred.
  • Examples of exterior materials include metal cans and aluminum laminate film packs.
  • the battery has a square shape, a cylindrical shape, a coin shape, and the like, but the separator of the present disclosure is suitable for any shape.
  • a method for producing a non-aqueous secondary battery according to the present disclosure includes a method of performing a heat press treatment (referred to as “dry heat press” in the present disclosure) without impregnating a separator with an electrolyte and bonding the separator to an electrode.
  • a production method including impregnating the separator with an electrolytic solution and performing a heat press treatment referred to as “wet heat press” in the present disclosure) to adhere to the electrode.
  • a manufacturing method in which dry heat pressing is performed is preferable.
  • the manufacturing method includes, for example, a stacking process for manufacturing a laminate in which the separator of the present disclosure is disposed between a positive electrode and a negative electrode, and a dry bonding process in which a dry heat press is performed on the stack to bond the electrode and the separator.
  • the method of disposing the separator between the positive electrode and the negative electrode may be a method of laminating at least one layer of the positive electrode, the separator, and the negative electrode in this order (so-called stack method).
  • stack method A method of overlapping in order and rolling in the length direction may be used.
  • the dry adhesion step may be performed before the laminate is accommodated in an exterior material (for example, an aluminum laminate film pack) or may be performed after the laminate is accommodated in the exterior material. That is, the laminate in which the electrode and the separator are bonded by dry heat pressing may be accommodated in the exterior material, and after the laminate is accommodated in the exterior material, dry heat press is performed from above the exterior material to remove the electrode and separator. It may be adhered.
  • an exterior material for example, an aluminum laminate film pack
  • the pressing temperature in the dry bonding step is preferably 70 ° C. to 120 ° C., more preferably 75 ° C. to 110 ° C., and still more preferably 80 ° C. to 100 ° C. Within this temperature range, the adhesion between the electrode and the separator is good, and since the separator can expand appropriately in the width direction, short-circuiting of the battery is unlikely to occur.
  • the press pressure in the dry bonding step is preferably 0.5 kg to 40 kg as a load per 1 cm 2 of electrode.
  • the pressing time is preferably adjusted according to the pressing temperature and pressing pressure, and is adjusted, for example, in the range of 0.5 minutes to 60 minutes.
  • the laminate may be temporarily bonded by performing room temperature press (pressurization at room temperature) on the laminate before dry heat pressing.
  • an electrolytic solution is injected into the exterior material containing the laminate, and the exterior material is sealed.
  • the laminate may be further wet heat pressed from above the exterior material.
  • the inside of the exterior body is preferably in a vacuum state. Examples of a method for sealing the exterior material include a method in which the opening of the exterior material is bonded with an adhesive, and a method in which the opening of the exterior material is heated and pressed to be thermocompression bonded.
  • the separator and the non-aqueous secondary battery of the present disclosure will be described more specifically with reference to examples.
  • the materials, amounts used, ratios, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present disclosure. Therefore, the range of the separator and the nonaqueous secondary battery of the present disclosure should not be limitedly interpreted by the specific examples shown below.
  • composition of polyvinylidene fluoride resin 20 mg of a polyvinylidene fluoride resin was dissolved in 0.6 ml of heavy dimethyl sulfoxide at 100 ° C., a 19 F-NMR spectrum was measured at 100 ° C., and the composition of the polyvinylidene fluoride resin was determined from the NMR spectrum.
  • Weight average molecular weight of polyvinylidene fluoride resin The weight average molecular weight (Mw) of the polyvinylidene fluoride resin was determined using a gel permeation chromatography analyzer (JASCO GPC-900), two Tosoh TSKgel SUPER AWM-H columns, and N, N solvents. -Measured as a molecular weight in terms of polystyrene using dimethylformamide under conditions of a temperature of 40 ° C and a flow rate of 10 ml / min.
  • the glass transition temperature of the resin was determined from a differential scanning calorimetry curve (DSC curve) obtained by performing differential scanning calorimetry (DSC).
  • the glass transition temperature is a temperature at a point where a straight line obtained by extending the base line on the low temperature side to the high temperature side and a tangent line of the curve of the step-like change portion and the maximum gradient.
  • the film thickness ( ⁇ m) of the porous substrate and the separator was determined by measuring 20 points with a contact-type thickness meter (LITEMATIC, Mitutoyo Corp.) and averaging them.
  • the measurement terminal was a cylindrical terminal having a diameter of 5 mm, and was adjusted so that a load of 7 g was applied during the measurement.
  • Gurley value The Gurley value (second / 100 cc) of the porous substrate and the separator was measured using a Gurley type densometer (Toyo Seiki G-B2C) according to JIS P8117: 2009.
  • the porosity (%) of the porous substrate and the porous layer was determined according to the following formula.
  • ⁇ is a porosity (%)
  • Ws is a basis weight (g / m 2 )
  • ds is a true density (g / cm 3 )
  • t is a thickness ( ⁇ m).
  • ⁇ ⁇ 1-Ws / (ds ⁇ t) ⁇ ⁇ 100
  • Adhesive tape was applied to one surface of the separator (when the adhesive was applied, the length direction of the adhesive tape was matched with the MD direction of the separator), and the separator was cut out in the TD direction 1.2 cm and MD direction 7 cm together with the adhesive tape. It was.
  • the adhesive tape was peeled off together with the porous layer directly below, and the two separated ends were held by Tensilon (RTC-1210A manufactured by Orientec Co., Ltd.), and a T-shaped peel test was performed.
  • an adhesive tape is used as a support body for peeling a porous layer from a porous base material.
  • the tensile speed of the T-peel test was 20 mm / min, and the load (N) when the porous layer was peeled from the porous substrate was measured. After the start of measurement, loads from 10 mm to 40 mm were sampled at intervals of 0.4 mm, the average was calculated, converted to a load per 10 mm width (N / 10 mm), and the measured values of three test pieces were averaged, The peel strength (N / 10 mm) was used.
  • Adhesive strength between positive electrode and first porous layer 89.5 g of lithium cobaltate powder as a positive electrode active material, 4.5 g of acetylene black as a conductive auxiliary agent, and 6 g of polyvinylidene fluoride as a binder are mixed with N-methyl so that the concentration of polyvinylidene fluoride is 6% by mass. -Dissolved in pyrrolidone and stirred in a double-arm mixer to prepare a positive electrode slurry. This positive electrode slurry was applied to one side of an aluminum foil having a thickness of 20 ⁇ m, dried and pressed to obtain a positive electrode having a positive electrode active material layer.
  • the positive electrode obtained above was cut into a width of 1.5 cm and a length of 7 cm, and a separator was cut into a TD direction of 1.8 cm and an MD direction of 7.5 cm.
  • the first porous layer of the separator was stacked to face the positive electrode, and was hot-pressed under conditions of a temperature of 85 ° C., a pressure of 1.0 MPa, and a time of 10 seconds to bond the positive electrode and the separator, and this was used as a test piece. .
  • the separator is slightly peeled off from the positive electrode, and the two separated ends are held by Tensilon (RTC-1210A manufactured by Orientec Co., Ltd.) to conduct a T-shaped peel test. went.
  • the tensile speed of the T-peel test is 20 mm / min
  • the load (N) when the separator peels from the positive electrode is measured
  • the load from 10 mm to 40 mm is sampled at intervals of 0.4 mm after the measurement is started, and the average is calculated.
  • the measured values of the three test pieces were averaged to obtain the adhesive strength (N) between the positive electrode and the first porous layer.
  • Tables 1 to 4 show percentages (%) obtained by dividing the adhesive strength of the separators of Examples and Comparative Examples by the adhesive strength of the separators of Comparative Example 1.
  • Adhesive strength between negative electrode and second porous layer 300 g of artificial graphite as negative electrode active material, 7.5 g of water-soluble dispersion containing 40% by mass of modified styrene-butadiene copolymer as binder, 3 g of carboxymethyl cellulose as thickener, and appropriate amount of water The mixture was stirred with a type mixer to prepare a negative electrode slurry. This negative electrode slurry was applied to one side of a 10 ⁇ m thick copper foil, dried and pressed to obtain a negative electrode having a negative electrode active material layer.
  • the negative electrode obtained above was cut into a width of 1.5 cm and a length of 7 cm, and the separator was cut into a TD direction of 1.8 cm and an MD direction of 7.5 cm.
  • the second porous layer of the separator was stacked facing the negative electrode, and was hot-pressed under conditions of a temperature of 85 ° C., a pressure of 1.0 MPa, and a time of 10 seconds to bond the negative electrode and the separator, and this was used as a test piece. .
  • the test piece was subjected to a T-shaped peel test in the same manner as in [First embodiment: Adhesive strength between positive electrode and first porous layer], and the adhesive strength between negative electrode and second porous layer (N). Asked.
  • Tables 1 to 4 show percentages (%) obtained by dividing the adhesive strength of the separators of Examples and Comparative Examples by the adhesive strength of the separators of Comparative Example 1.
  • the conditions for hot pressing were a temperature of 90 ° C., a load of 20 kg per 1 cm 2 of electrode, and a pressing time of 2 minutes.
  • an electrolytic solution (1 mol / L LiPF 6 -ethylene carbonate: ethyl methyl carbonate [mass ratio 3: 7]) was injected into the pack, and the laminate was impregnated with the electrolytic solution. was sealed under vacuum to obtain a battery.
  • the battery was charged and discharged for 300 cycles under an environment of a temperature of 30 ° C.
  • the charging was a constant current and constant voltage charging of 1C and 4.2V, and the discharging was a constant current discharging of 1C and 2.75V cut-off.
  • the discharge capacity at the 300th cycle was divided by the initial capacity, the average of 10 batteries was calculated, and the obtained value (%) was taken as the capacity retention rate.
  • a battery was produced in the same manner as the battery production in [Cycle characteristics (capacity maintenance ratio)].
  • the battery was charged and discharged in an environment at a temperature of 25 ° C., the discharge capacity when discharged at 0.2 C and the discharge capacity when discharged at 2 C were measured, the latter was divided by the former, and 10 batteries were The average was calculated, and the obtained value (%) was taken as the load characteristic.
  • the charging conditions were 0.2 C, 4.2 V constant current constant voltage charging for 8 hours, and the discharging conditions were 2.75 V cut-off constant current discharging.
  • polyvinylidene fluoride resin VDF-HFP copolymer, HFP unit content 6 mass%, weight average
  • acrylic resin methyl methacrylate-methacrylic acid copolymer, polymerization ratio [mass ratio] 90:10, weight average molecular weight 85,000, glass transition temperature 80 ° C.
  • a second coating solution for forming a two-porous material was prepared.
  • the mass ratio of the polyvinylidene fluoride resin and the acrylic resin contained in the second coating liquid was 75:25, and the resin concentration of the second coating liquid was 5.0 mass%.
  • the first coating liquid is applied to one side of the polyethylene microporous membrane (film thickness 9.0 ⁇ m, Gurley value 150 seconds / 100 cc, porosity 43%), which is a porous substrate, and the second coating is applied to the other side.
  • Example 2 A separator was prepared in the same manner as in Example 1 except that the acrylic resin for preparing the second coating solution was changed to a vinyl acetate resin (polyvinyl acetate, weight average molecular weight 15,000, glass transition temperature 30 ° C.). Produced.
  • a vinyl acetate resin polyvinyl acetate, weight average molecular weight 15,000, glass transition temperature 30 ° C.
  • Example 3 A separator was prepared in the same manner as in Example 1 except that the acrylic resin for preparing the second coating solution was changed to a vinyl chloride resin (polyvinyl chloride, weight average molecular weight 20,000, glass transition temperature 40 ° C.). .
  • a vinyl chloride resin polyvinyl chloride, weight average molecular weight 20,000, glass transition temperature 40 ° C.
  • Examples 4 to 9 A separator was produced in the same manner as in Example 1 except that the contents of the polyvinylidene fluoride resin and acrylic resin contained in the second coating solution were changed as shown in Table 1.
  • Example 10 To the first coating liquid and the second coating liquid, magnesium hydroxide particles (volume average particle diameter of primary particles 0.8 ⁇ m, BET specific surface area 6.8 m 2 / A separator was prepared in the same manner as in Example 1 except that g) was dispersed.
  • Example 11 To the first coating liquid and the second coating liquid, magnesium hydroxide particles (volume average particle diameter of primary particles 0.8 ⁇ m, BET specific surface area 6.8 m 2 / A separator was prepared in the same manner as in Example 2 except that g) was dispersed.
  • Example 12 To the first coating liquid and the second coating liquid, magnesium hydroxide particles (volume average particle diameter of primary particles 0.8 ⁇ m, BET specific surface area 6.8 m 2 / A separator was prepared in the same manner as in Example 3 except that g) was dispersed.
  • Examples 13 to 14 Except that the contents of the resin and magnesium hydroxide particles contained in the first coating liquid and the contents of the resin and magnesium hydroxide particles contained in the second coating liquid were changed as shown in Table 2, A separator was prepared in the same manner as in Example 10.
  • Example 1 except that the polyvinylidene fluoride resin for preparing the first coating liquid was changed to another polyvinylidene fluoride resin (VDF-HFP copolymer having the composition and weight average molecular weight shown in Table 3). In the same manner, a separator was produced.
  • VDF-HFP copolymer having the composition and weight average molecular weight shown in Table 3
  • Example 19 Example 1 except that the polyvinylidene fluoride resin for preparing the second coating solution was changed to another polyvinylidene fluoride resin (VDF-HFP copolymer having the composition and weight average molecular weight shown in Table 3). In the same manner, a separator was produced.
  • VDF-HFP copolymer having the composition and weight average molecular weight shown in Table 3
  • Tables 1 to 4 show the physical properties and evaluation results of the separators of Examples 1 to 19 and Comparative Examples 1 to 8.
  • Example 102 A separator was produced in the same manner as in Example 101 except that the acrylic resin was changed to a vinyl acetate resin (polyvinyl acetate, weight average molecular weight 15,000, glass transition temperature 30 ° C.).
  • Example 103 A separator was produced in the same manner as in Example 101 except that the acrylic resin was changed to a vinyl chloride resin (polyvinyl chloride, weight average molecular weight 20,000, glass transition temperature 40 ° C.).
  • a vinyl chloride resin polyvinyl chloride, weight average molecular weight 20,000, glass transition temperature 40 ° C.
  • Example 104 to 109 A separator was produced in the same manner as in Example 101 except that the mass ratio of the polyvinylidene fluoride resin and the acrylic resin contained in the coating liquid was changed as shown in Table 5.
  • Example 110 Except that magnesium hydroxide particles (volume average particle size of primary particles 0.8 ⁇ m, BET specific surface area 6.8 m 2 / g) were further dispersed in the coating solution so as to have the contents shown in Table 6. A separator was produced in the same manner as in Example 101.
  • Example 111 Except that magnesium hydroxide particles (volume average particle size of primary particles 0.8 ⁇ m, BET specific surface area 6.8 m 2 / g) were further dispersed in the coating solution so as to have the contents shown in Table 6. A separator was produced in the same manner as in Example 102.
  • Example 112 Except that magnesium hydroxide particles (volume average particle size of primary particles 0.8 ⁇ m, BET specific surface area 6.8 m 2 / g) were further dispersed in the coating solution so as to have the contents shown in Table 6. A separator was produced in the same manner as in Example 103.
  • Example 113 to 114 A separator was produced in the same manner as in Example 110 except that the contents of the polyvinylidene fluoride resin, the acrylic resin, and the magnesium hydroxide particles were changed as shown in Table 6.
  • Example 115 to 118 A separator was produced in the same manner as in Example 101 except that the polyvinylidene fluoride resin was changed to another polyvinylidene fluoride resin (VDF-HFP copolymer having the composition and weight average molecular weight shown in Table 6). .
  • Example 101 A separator was produced in the same manner as in Example 101 except that the coating liquid did not contain an acrylic resin.
  • Example 102 A separator was prepared in the same manner as in Example 110 except that the coating liquid did not contain an acrylic resin and the contents of the polyvinylidene fluoride resin and magnesium hydroxide particles were changed as shown in Table 7.
  • Example 101 A separator Except for changing the polyvinylidene fluoride resin to another polyvinylidene fluoride resin (VDF-HFP copolymer or polyvinylidene fluoride having the composition and weight average molecular weight shown in Table 7), the same as Example 101 A separator was produced.
  • Example 104 and 107 Except for changing the polyvinylidene fluoride resin to another polyvinylidene fluoride resin (VDF-HFP copolymer or polyvinylidene fluoride having the composition and weight average molecular weight shown in Table 7), the same as Example 102 A separator was produced.
  • VDF-HFP copolymer or polyvinylidene fluoride having the composition and weight average molecular weight shown in Table 7 the same as Example 102 A separator was produced.
  • Example 105 and 108 Except for changing the polyvinylidene fluoride resin to another polyvinylidene fluoride resin (VDF-HFP copolymer or polyvinylidene fluoride having the composition and weight average molecular weight shown in Table 7), the same as Example 103 A separator was produced.
  • VDF-HFP copolymer or polyvinylidene fluoride having the composition and weight average molecular weight shown in Table 7 the same as Example 103 A separator was produced.
  • Tables 5 to 7 show the physical properties and evaluation results of the separators of Examples 101 to 118 and Comparative Examples 101 to 108.

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